This invention concerns the art of catalyst regeneration. More specifically, the present invention concerns a method for burning nitrogen-containing coke off coke-containing particulate catalyst while avoiding contamination of flue gas formed in burning the coke.
Catalytic cracking systems employ catalyst in a moving bed or a fluidized bed. Catalytic cracking is carried out in the absence of externally supplied molecular hydrogen, in contrast to hydrocracking, in which molecular hydrogen is added during the cracking step. In catalytic cracking, an inventory of particulate catalyst is continuously cycled between a cracking reactor and a catalyst regenerator. In a fluidized catalytic cracking (FCC) system, hydrocarbon feed is contacted with catalyst particles in a hydrocarbon cracking zone, or reactor, at a temperature of about 425.degree. C.-600.degree. C., usually 460.degree. C.-560.degree. C. The reactions of hydrocarbons at the elevated operating temperature result in deposition of carbonaceous coke on the catalyst particles. The resulting fluid products are separated from the coke-deactivated, spent catalyst and are withdrawn from the reactor. The coked catalyst particles are stripped of volatiles, usually by means of steam, and passed to the catalyst regeneration zone. In the catalyst regenerator, the spent catalyst is contacted with a predetermined amount of molecular oxygen. A desired portion of the coke is burned off the catalyst, restoring catalyst activity and simultaneously heating the catalyst to, e.g., 540.degree. C.-815.degree. C., usually 590.degree. C.-730.degree. C. Flue gas formed by combustion of coke in the catalyst regenerator may be treated for removal of particulates and for conversion of carbon monoxide, after which the flue gas is normally discharged into the atmosphere.
Most FCC units now use zeolite-containing catalyst having high activity and selectivity. Zeolite-type catalyst have a particularly high activity and selectivity when the concentration of coke on the catalyst after regeneration is relatively low, so that it is generally desirable to regenerate zeolite-containing catalysts to as low a residual carbon level as is possible. It is also normally desirable to burn carbon monoxide as completely as possible within the catalyst regeneration system to conserve heat. Heat conservation is especially important when the concentration of coke on the spent catalyst is relatively low as a result of high catalyst selectivity. Among the ways suggested to decrease the amount of carbon on regenerated catalyst and to burn carbon monoxide in a manner which provides process heat, is carrying out carbon monoxide combustion in a dense-phase catalyst bed in the catalyst regenerator using an active, combustion-promoting metal. Metals have been used either as an integral component of the cracking catalyst particles or as a component of a discrete particulate additive, in which the active metal is associated with a support other than the catalyst particles.
Various ways of employing carbon monoxide combustion-promoting metals in cracking systems have been suggested. In U.S. Pat. No. 2,647,860, it is proposed to add 0.1-1 weight percent chromic oxide to a cracking catalyst to promote combustion of carbon monoxide to carbon dioxide and to prevent afterburning. In U.S. Pat. No. 3,808,121, it is proposed to introduce relatively large-sized particles containing a carbon monoxide combustion-promoting metal into a cracking catalyst regenerator. The circulating particulate solids inventory, comprised of relatively small-sized catalyst particles, is cycled between the cracking reactor and the catalyst regenerator, while the combustion-promoting particles remain in the regenerator because of their size. Oxidation-promoting metals such as cobalt, copper, nickel, manganese, copper-chromite, etc., impregnated on an inorganic oxide such as alumina, are disclosed. Belgian Patent Publication No. 820,181 suggests using catalyst particles in platinum, palladium, iridium, rhodium, osmium, ruthenium or rhenium to promote carbon monoxide oxidation in a catalyst regenerator. An amount of the metal between a trace and 100 parts per million is to be added to the catalyst particle, either during catalyst manufacture or during the cracking operation, as by addition of a compound of the combustion-promoting metal to the hydrocarbon feed. Addition of the promoting metal to the cracking system is said by the publication to decrease product selectivity in the cracking step by substantially increasing coke and hydrogen formation. Catalyst particles containing the promoter metal can be used alone or can be circulated in physical mixture with catalyst particles free of the combustion-promoting metal. U.S. Pat. No. 4,072,600 and No. 4,093,535 disclose the use of combustion-promoting metals in cracking catalysts in concentrations of 0.01 to 50 ppm, based on total catalyst inventory.
One problem encountered in some cracking operations using metal-promoted, complete carbon monoxide combustion-type regeneration has been the generation of undesirable nitrogen oxides (NO.sub.x) in the flue gas formed by burning coke. The present invention is directed, in part, toward providing a catalyst regeneration system, which accomplishes complete coke removal and complete carbon monoxide combustion within a catalyst regeneration system, while substantially decreasing the concentration of nitrogen oxide present in flue gas formed by burning coke.
Representative of catalyst regeneration patent literature previously published are the following patents: U.S. Pat. No. 3,909,392 describes a scheme for enhancing carbon monoxide combustion by thermal means. Catalyst is used a heat sink for the increased heat production. British Patent Publication No. 2,001,545 describes a two-stage system for a regenerating catalyst, with partial catalyst regeneration being carried out in the first stage and further more complete regeneration being carried out in the second stage with a separate regeneration gas. U.S. Pat. No. 3,767,566 describes a two-stage regeneration scheme in which partial regeneration takes place in an entrained catalyst bed, and secondary, more complete regeneration takes place in a dense fluidized catalyst bed. A somewhat similar regeneration operation is described in U.S. Pat. No. 3,902,990, which discusses the use of several stages of regeneration, with dilute- and dense-phase beds of catalysts being employed, and with the use of plural streams of regeneration gas. U.S. Pat. No. 3,926,843 describes a plural-stage regeneration scheme in which dilute-phase and dense-phase coke burning are performed. British Patent Publication No. 1,499,682 discloses use of a combustion-promoting metal for enhancing carbon monoxide combustion. None of the above cited patents provides a method for forming a flue gas having low concentrations of both carbon monoxide and nitrogen oxides, while accomplishing essentially complete removal of coke from the catalyst.